Coordination Networks with Flexible Ligands Based on Silver(I) Salts: Complexes of 1,3-Bis(phenylthio)propane with Silver(I) Salts of PF₆^-, CF₃COO^-, CF₃CF₂COO^-, CF₃CF₂CF₂COO^-, <i>p</i>-TsO^-, and CF₃SO₃^-

The synthesis and characterization of nine coordination networks based on 1,3-bis(phenylthio)propane, L3, and silver(I) salts of PF6- (1), CF3COO- (2), CF3CF2COO- (3), CF3CF2CF2COO- (4), p-TsO- (5, 6), and CF3SO3- (7−9) are reported. Only 1 and other “isostructural” complexes with weakly coordinating anions such as ClO4- and SbF6- are of the host−guest type. In all the other complexes, the anions and the acetone molecules, when present, are coordinated to the metal. Most of the complexes studied here form a 2D-coordination network. Only 4 and 5 adopt a polymer-like chain structure. The packing of the chains of 4 is pseudohexagonal compact, while that of 5 is of the centered type. In complex 1, the silver atom is tetrahedrally coordinated to the sulfur atoms of four different ligands. The PF6- anions and acetone molecules, sandwiched between silver−ligand cationic sheets, are held through van der Waals interactions. In each of the three perfluorocarboxylates (2−4), two silver atoms are joined by the anions in a diatomic bridging mode. The Ag···Ag distances are sufficiently short to indicate weak metal···metal interactions. The dimeric units in 2 and 3 are interconnected through the ligands, thereby generating a 2D-network of neutral sheets, while, in 4, the dimeric units are bound to four ligands and a 1D-coordination polymer is generated. In the case of the sulfonate anions (p-TsO- and CF3SO3-), the crystallization solvent influences the structure adopted. Thus, in 5, 7, and 9 obtained from petroleum ether, or other nonpolar solvents, two silver atoms are bound in a double-bridge fashion, while a monobridge mode is noted for 6 and 8, both recrystallized from diethyl ether. In 8, both bridging types are observed. The thermogravimetric investigation, in the room temperature−450 °C interval, of complexes 1, 3, and 7, which incorporate acetone molecules in their crystal structures, reveals a two-step weight loss for 1 (the acetone molecules are lost first followed by the ligands, leaving behind the silver salt), while complexes 3 and 7 decompose in a single step to metallic silver.